Microwave-based recovery of hydrocarbons and fossil fuels

ABSTRACT

The present invention provides methods for decomposing and extracting compositions for the recovery of petroleum-based materials from composites comprising those petroleum-based materials, comprising subjecting the compositions and/or composites to microwave radiation, wherein the microwave radiation is in the range of from about 4 GHz to about 18 GHz. The present invention also provides for products produced by the methods of the present invention and for apparatuses used to perform the methods of the present invention.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a 35 U.S.C. §121 divisional of U.S. patentapplication Ser. No. 11/610,823, filed Dec. 14, 2006, and it also claimsthe benefit of U.S. Provisional Patent Application No. 60/750,098,“Method for Using Microwave Radiation”, filed Dec. 14, 2005, theentirety of each application is incorporated by reference herein.

FIELD OF THE INVENTION

The present invention relates to methods and apparatuses for usingmicrowave radiation and more particularly, to methods and apparatusesfor decomposing compositions comprising petroleum-based materials.

BACKGROUND OF THE INVENTION

Petroleum-based materials are integral to the world's economy and demandfor such fuels and consumer products is increasing. As the demand rises,there is a need to efficiently and economically extract petroleum-basedmaterials to fulfill that demand. As such, it would be advantageous tonot only be able to extract petroleum-based materials from the earth,but to also recycle consumer products to recapture those petroleum-basedmaterials.

Worldwide oil consumption is estimated at seventy-three million barrelsper day and growing. Thus, there is a need for sufficient oil supplies.Tar sands, oil sands, oil shales, oil cuttings, and slurry oil containlarge quantities of oil, however, extraction of oil from these materialsis costly and time-consuming and generally does not yield sufficientquantities of usable oil.

Soil contaminated with petroleum products is an environmental hazard,yet decontamination of petroleum-tainted soil is time-consuming andexpensive.

Furthermore, it has been estimated that 280 million gallons of oil-basedproducts such as plastics go into landfills each day in the UnitedStates. It would be desirable to recapture and recycle the raw materialsof these products.

Scrap vehicle tires are a significant problem worldwide and theirdisposal presents significant environmental and safety hazards,including fires, overflowing landfills, and atmospheric pollution. Whilethere are a number of existing applications for these tires, includingtire-derived fuels, road construction, and rubber products, theseapplications are insufficient to dispose of all the available scraptires. The major components of tires are steel, carbon black, andhydrocarbon gases and oils, which are commercially desirable. As such,it is advantageous to develop processes for the recovery of theseproducts from scrap vehicles tires. Prior art methods of decomposingscrap vehicle tires do not produce commercial-grade carbon black andrequire high temperatures and extended exposure times for recovery ofthe hydrocarbon components.

Efforts to recycle tires using microwave technology has been describedin U.S. Pat. Nos. 5,507,927 and 5,877,395 to Emery. Efforts to recoverpetroleum from petroleum-impregnated media has been described in U.S.Pat. Nos. 4,817,711 and 4,912,971 to Jeambey. Efforts to decomposeplastics using microwave radiation has been described in U.S. Pat. No.5,084,140 to Holland. The prior work has involved the use ofsingle-frequency microwave radiation. Single-frequency microwaveradiation is a slow process that does not provide uniform heating.Moreover, single-frequency microwave radiation typically results inarcing on metal components.

Thus, there is a need for methods and apparatuses for the recycling ofpetroleum-based compositions and for the recovery of petroleum-basedmaterials from composites containing petroleum-based materials. Theinvention is directed to these and other important needs.

SUMMARY OF THE INVENTION

The present invention provides methods for decomposing compositionscomprising carbon-based materials comprising subjecting the compositionsto microwave radiation for a time sufficient to at least partiallydecompose the composition, wherein the microwave radiation comprises atleast one frequency component in the range of from about 4 GHz to about18 GHz.

The present invention provides methods for decomposing compositionscomprising petroleum-based materials comprising subjecting thecompositions to microwave radiation for a time sufficient to at leastpartially decompose the composition, wherein the microwave radiationcomprises at least one frequency component in the range of from about 4GHz to about 18 GHz.

The present invention further provides methods for recovery ofpetroleum-based materials from composites comprising thosepetroleum-based materials. The methods of the present invention includesubjecting the composite to microwave radiation for a time sufficient toextract the petroleum-based material, wherein the microwave radiationcomprises at least one frequency component in the range of from about 4GHz to about 18 GHz.

The present invention also provides for products produced by the methodsof the present invention.

The present invention additionally provides apparatuses for decomposingcompositions comprising petroleum-based materials. The apparatuses ofthe present invention comprise a microwave radiation generator, whereinthe generator is capable of applying microwave radiation characterizedas having at least one frequency component in the range of from 4 GHz toabout 18 GHz, and at least one container to collect decomposedcomponents from the compositions. The present invention further providesapparatuses for extracting petroleum-based materials from compositescomprising the petroleum-based material. These apparatuses comprise amicrowave radiation generator, wherein the generator is capable ofapplying microwave radiation characterized as having at least onefrequency component in the range of from 4 GHz to about 18 GHz, and atleast one container to collect decomposed components from the composite.

The general description and the following detailed description areexemplary and explanatory only and are not restrictive of the invention,as defined in the appended claims. Other aspects of the presentinvention will be apparent to those skilled in the art in view of thedetailed description of the invention as provided herein.

BRIEF DESCRIPTION OF THE DRAWINGS

The summary, as well as the following detailed description, is furtherunderstood when read in conjunction with the appended drawings. For thepurpose of illustrating the invention, there are shown in the drawingsexemplary embodiments of the invention; however, the invention is notlimited to the specific methods, compositions, and devices disclosed. Inaddition, the drawings are not necessarily drawn to scale. In thedrawings:

FIGS. 1A-1G illustrate an embodiment of the present invention directedto processing tire cuttings using microwaves to recover fuel oil;

FIG. 2A is an elevation view, axial direction, of a microwave reactorsuitable for processing oil cuttings according to an aspect of thepresent invention;

FIG. 2B illustrates an elevation view of the microwave reactor of FIG.2A, longitudinal direction;

FIG. 2C illustrates an elevation view of the microwave device andcontrol room suitable for generating microwaves and propagating the samethrough waveguides;

FIGS. 3A-3B illustrate several embodiments of the present invention forextracting petroleum-based materials from oil slurry;

FIG. 4A illustrates an elevation view of a microwave reactor systemsuitable for processing shale rock, tar sands, drill cuttings, and thelike;

FIG. 4B provides a plan view of FIG. 4A;

FIG. 4C is an elevation view of the microwave reactor system along theaxis 406, the near end being the exit discharge screw feed systemsection 416;

FIG. 4D illustrates a suitable microwave device control room,waveguides, and vacuum pumps suitable for use with the systemillustrated in FIG. 4A;

FIG. 4E illustrates an optional hopper elevator for transportingmaterial into the inlet feed section 402;

FIGS. 4F and 4G illustrate three horizontal microwave reactor systemsoperating in parallel;

FIG. 4H illustrates additional microwave generators, waveguides andvacuum pumps for operating the three horizontal microwave reactorsillustrated in FIGS. 4F and 4G;

FIG. 5A is an illustration of one embodiment of the present inventionfor extracting petroleum-based materials from heavy oil contained in oilwells;

FIG. 5B is an illustration of one embodiment of the present inventionfor extracting petroleum-based materials from oil shale, in situ;

FIG. 5C illustrates the separation of crude oil using a fractionatingtower into its component products;

FIG. 6 is an illustration of one embodiment of the present invention forextracting petroleum-based materials from tar sands, oil sands and shalerock;

FIG. 7 is an schematic of one embodiment of the present invention fordecomposing vehicle tires;

FIG. 8A is a plan view of an oil platform incorporating a drill cuttingsmicrowave processing unit;

FIG. 8B illustrates an elevation view of the oil platform in FIG. 8A;

FIG. 8C illustrates a vertical and horizontal configurations of thedrill cuttings microwave processing unit suitable for use in the oilplatform illustrated in FIG. 8A;

FIG. 9A is a depiction of an electron microscope photograph of carbonblack produced by the method of the present invention;

FIG. 9B is a depiction of an electron microscope photograph of carbonblack produced by the method of the present invention;

FIG. 9C is a depiction of an electron microscope photograph of carbonblack produced by the method of the present invention; and

FIGS. 10A-10E illustrate an additional embodiment of a drum reactorsystem for processing materials containing hydrocarbons.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention may be understood more readily by reference to thefollowing detailed description taken in connection with the accompanyingfigures and examples, which form a part of this disclosure. It is to beunderstood that this invention is not limited to the specific devices,methods, applications, conditions or parameters described and/or shownherein, and that the terminology used herein is for the purpose ofdescribing particular embodiments by way of example only and is notintended to be limiting of the claimed invention. Also, as used in thespecification including the appended claims, the singular forms “a,”“an,” and “the” include the plural, and reference to a particularnumerical value includes at least that particular value, unless thecontext clearly dictates otherwise. The term “plurality”, as usedherein, means more than one. When a range of values is expressed,another embodiment includes from the one particular value and/or to theother particular value. Similarly, when values are expressed asapproximations, by use of the antecedent “about,” it will be understoodthat the particular value forms another embodiment. All ranges areinclusive and combinable.

It is to be appreciated that certain features of the invention whichare, for clarity, described herein in the context of separateembodiments, may also be provided in combination in a single embodiment.Conversely, various features of the invention that are, for brevity,described in the context of a single embodiment, may also be providedseparately or in any subcombination. Further, reference to values statedin ranges include each and every value within that range.

“Sweeping,” as the term is used herein, is defined as the application ofa plurality of radiation frequencies over a period of time.

“Pulsing,” as used herein, means subjecting the composition to microwaveradiation for a period of time, followed by periods of time wherein thecomposition is not subjected to microwave radiation.

“Oil,” as used herein, means any hydrocarbon or petroleum-based oil.

“Gas,” as used herein, includes any hydrocarbon-based material that isin the gaseous state at atmospheric temperature and pressure andincludes, but is not limited to, methane, ethane, propane, butane,isobutene, or mixtures thereof.

“Carbon black,” as used herein, includes any grade ofcommercially-acceptable carbon black, including, but not limited to,rubber black.

“Oil sands,” also known as “tar sands,” are deposits of bitumen, a heavyblack viscous oil.

“Oil shale” is sedimentary rock containing a high proportion of Kerogen,which, when heated, can be converted into oil.

“Slurry oil” is refinery waste oil.

“Oil cuttings” are the waste product generated during the drilling ofoil wells. Examples of oil cuttings include, but are not limited to,bits and pieces of oil-soaked soil and rock.

“Hydrocarbons” are compositions that comprise carbon and hydrogen.

“Carbon-based” refers to matter that comprises carbon.

“Decompose” and “decomposing” refers to a process whereby matter isbroken down to smaller constituents. For example, solids can be brokendown into particles, liquids, vapors, gases, or any combination thereof;rubbery materials can be broken down into liquids, vapors, gases, or anycombination thereof; viscous liquids can be broken down to lowerviscosity liquids, vapors, gases, or any combination thereof; liquidscan be broken down to vapors, gases, or any combination thereof;composite materials comprising inorganic solids and trapped organicmatter can be broken down to inorganic solids and released organicvapors and gases, and the like.

1 Torr=1 mm Hg=1 millimeter mercury.

Methods for decomposing compositions comprising petroleum-basedmaterials are set forth herein. The compositions used in the presentinvention contemplate any composition comprised of petroleum-based,carbon-based and various hydrocarbon materials. The petroleum-basedmaterials may be present in the composition in amounts ranging fromabout 1% to 100%, by weight, based on the weight of the composition.Preferably, the composition is a vehicle tire. In other embodiments, thecomposition comprises plastic, which includes, but is not limited toethylene (co)polymer, propylene (co)polymer, styrene (co)polymer,butadiene (co)polymer, polyvinyl chloride, polyvinyl acetate,polycarbonate, polyethylene terephthalate, (meth)acrylic (co)polymer, ora mixture thereof. A variety of natural and synthetic resins and rubberscan also be decomposed according to the methods described herein.Various carbon-based materials that can also be processed according tothe inventions described herein include coal, such as anthracite coaland bituminous coal.

In one embodiment, the composition is subjected to microwave radiationfor a time sufficient to at least partially decompose the composition.The microwave radiation can be in the range of from about 4.0 and about12.0 GHz. Other ranges can also be used, for example, in the range offrom about 4 GHz to about 18 GHz, and more preferably in the range offrom about 12 GHz to about 18 GHz. For example, coal can be processed atfrequencies in the range of from about 4 GHz to about 18 GHz, and morepreferably in the range of from about 12 GHz to about 18 GHz.

In one embodiment, the composition is subjected to one or morepre-selected microwave radiation frequencies. Preferably, thepre-selected microwave radiation frequency will be the resonatingmicrowave frequency, i.e, the microwave radiation frequency at which thecomposition absorbs a maximum amount of microwave radiation. It has beendetermined that different compositions of the present invention willabsorb more or less microwave radiation, depending on the frequency ofthe microwave radiation applied. It has also been determined that thefrequency at which maximum microwave radiation is absorbed differs bycomposition. By using methods known in the art, a composition of thepresent invention can be subjected to different frequencies of microwaveradiation and the relative amounts of microwave radiation absorbed canbe determined. Preferably, the microwave radiation selected is thefrequency that comparatively results in the greatest amount of microwaveradiation absorption. In one embodiment, microwave radiation frequencyresulting in a comparative maximum absorption of microwave radiation bythe compositions of the present invention is in the range of from about4.0 and about 12.0 GHz. In others, particularly with respect to vehicletires, the microwave radiation frequency resulting in a comparativemaximum absorption of microwave radiation by the compositions of thepresent invention is in the range of from about 4.0 and about 7.2 GHz.In yet others, the microwave radiation frequency resulting in acomparative maximum absorption of microwave radiation by thecompositions of the present invention is in the range of from about 4.0and about 6.0 GHz.

The present invention also provides methods for subjecting a compositionto a sweeping range of microwave radiation frequencies for a timesufficient to at least partially decompose the composition. Preferably,variable frequency microwave (“VFM”) is used to sweep the compositions.VFM is described in U.S. Pat. No. 5,321,222 to Bible, et al. and U.S.Pat. No. 5,521,360 to Johnson, et al., incorporated herein by referencein their entireties. Unlike single frequency microwave radiation, VFMproduces a bandwidth of microwave radiation frequencies that are appliedsequentially to the composition. Consequentially, the field distributionwith VFM is substantially more uniform than the field distribution ofsingle microwave frequency radiation. The more uniform fielddistribution of VFM produces fewer hot spots, resulting in more uniformheating of the composition. Moreover, generally, no single frequency isapplied for longer than about 25 μs. The short duration of each appliedfrequency produces no build-up of charge, thus eliminating discharge, orarcing, typically observed during single frequency microwaveirradiation.

In some embodiments, particularly with respect to vehicle tires, therange of microwave radiation frequencies swept is in the range of fromabout 4.0 GHz to about 12.0 GHz. In certain embodiments, the range ofmicrowave radiation frequencies swept is in the range of from about 5.8GHz to about 7.0 GHz. In still others, the range of microwave radiationfrequencies swept is in the range of from about 7.9 GHz and 8.7 GHz. Insome embodiments, range of microwave radiation frequencies is in theC-Band frequency range, the C-Band frequency range encompassingmicrowave frequencies in the range of from about 4.0 GHz to about 8.0GHz. In other embodiments, the range of microwave radiation frequenciesis in the X-Band frequency range, the X-band frequency rangeencompassing microwave frequencies in the range of from about 8.0 GHz toabout 12.0 GHz.

Preferably, the sweeping of the range of microwave radiation frequenciesencompasses a pre-selected, resonating microwave radiation frequencycharacterized as having at least one frequency component in the range offrom about 4.0 GHz to about 12.0 GHz. This frequency can be selected byusing the methods described herein and techniques known in the art.Preferably, the bandwidth of the sweeping range of microwave radiationis about 4.0 GHz. More preferably, the range of microwave frequencieswith which the composition is swept, is about +/−2 GHz of thepre-selected microwave radiation frequency. For example, if thepre-selected microwave radiation frequency is 7.2 GHz, the compositionwould be swept with the range of microwave radiation frequenciesencompassing from about 5.2 to about 9.2 GHz. The microwave frequenciescan also be swept at about +/−1.5 GHz, or even +/−1.0 GHz, or even+/−0.5 GHz of the preselected microwave frequency.

Upon decomposition of the compositions subjected to the methods andapparatuses of the invention, flammable hydrocarbon-based gases arereleased. To reduce the risk of ignition, it is preferred that themethod be performed in an oxygen-deprived atmosphere. Preferably, thecomposition is exposed to less than about 12% oxygen. More preferably,the composition is exposed to less than about 8% oxygen. Even morepreferably, the composition is exposed to less than about 5% oxygen.

In one embodiment, the composition is exposed an inert gas atmosphere.Preferably, the inert gas is nitrogen, argon, or mixtures thereof.

In some embodiments, the composition is exposed to less than atmosphericpressure. Preferably, the composition is exposed to less than about 40Torr. More preferably, the composition is exposed to less than about 20Torr. Even more preferably, the composition is exposed to less thanabout 5 Torr. Without being bound by any particular theory or operation,it is believed that operating at sub-atmospheric pressures helps torecover hydrocarbon-based gases and prevents over-heating.

In one embodiment, the composition of the present invention forms avehicle tire. Using the methods of the present invention, the tire canbe decomposed to produce at least one of oil, gas, steel, sulfur, andcarbon black.

Over-exposure to microwave radiation and over-heating of the compositionof the present invention may result in the recovery ofnon-commercially-acceptable carbon black. Controlling the temperature ofthe composition during microwave irradiation prevents such over-exposureand over-heating to produce commercially-acceptable carbon black.Preferably, the temperature of the composition does not exceed about700° F. More preferably, the temperature of the composition does notexceed about 500° F. Even more preferably, the temperature of thecomposition does not exceed about 465° F.

In one embodiment, the temperature of the composition can be controlledwhile performing the method of the present invention by pulsing themicrowave radiation subjection. For example, microwave radiation can beapplied until the composition temperature reaches about 465° F., atwhich time, the application of microwave radiation can be stopped for atime sufficient for the composition to cool between about 5 to 25degrees. Once the composition has cooled, the application of microwaveradiation can be resumed. This process can be repeated, as necessary,until the composition is sufficiently decomposed.

Decomposition products obtained from the compositions using the methodsof the present invention may be refined and/or purified using techniquesknown in the art.

The present invention also provides methods for extractingpetroleum-based materials from composites comprising the petroleum-basedmaterials by subjecting the composites to microwave radiation for a timesufficient to extract the petroleum-based material. Preferably, themicrowave radiation is in the range of from about 4.0 and about 12.0GHz.

The composites are any material comprising petroleum-based materials,including, but not limited to, at least one of oil sands, oil shale,slurry oil, oil cuttings, and soil or sand contaminated withpetroleum-based materials. As used herein, “composites” also includes,but is not limited to, oil wells.

In one embodiment, the composite is subjected to one or morepre-selected microwave radiation frequencies. Preferably, thepre-selected microwave radiation frequency will be the resonatingmicrowave frequency, i.e, the microwave radiation frequency at which thecomposite absorbs a maximum amount of microwave radiation. It has beendetermined that different composites of the present invention willabsorb more or less microwave radiation, depending on the frequency ofthe microwave radiation applied. It has also been determined that thefrequency at which maximum microwave radiation is absorbed differs bycomposite. By using methods known in the art, a composite of the presentinvention can be subjected to different frequencies of microwaveradiation and the relative amounts of microwave radiation absorbed canbe determined. Preferably, the microwave radiation selected is thefrequency that comparatively results in the greatest amount of microwaveradiation absorption. In one embodiment, microwave radiation frequencyresulting in a comparative maximum absorption of microwave radiation bythe composite of the present invention is in the range of from about 4.0and about 12.0 GHz. In others, the microwave radiation frequencyresulting in a comparative maximum absorption of microwave radiation bythe composite of the present invention is in the range of from about 7.9and about 12.0 GHz. In yet others, the microwave radiation frequencyresulting in a comparative maximum absorption of microwave radiation bythe composite of the present invention is in the range of from about 7.9and about 8.7 GHz.

The present invention also provides methods for recovery ofpetroleum-based materials from composites comprising thosepetroleum-based materials, by subjecting the composite to a sweepingrange of microwave radiation frequencies for a time sufficient toextract the petroleum-based material, and wherein the range offrequencies of the microwave radiation is in the range of from about 4.0GHz to about 12.0 GHz. The composites are any material comprisingpetroleum-based materials, including, but not limited to, at least oneof oil sands, oil shale, slurry oil, oil cuttings and soil or sandcontaminated with petroleum-based materials.

Preferably, variable frequency microwave (“VFM”) is used to sweep thecomposites. VFM is described in U.S. Pat. No. 5,321,222 to Bible, et al.and U.S. Pat. No. 5,521,360 to Johnson, et al., incorporated herein byreference in their entireties. Unlike single frequency microwaveradiation, VFM produces a bandwidth of microwave radiation frequenciesthat are applied sequentially to the composite. Consequentially, thefield distribution with VFM is substantially more uniform than the fielddistribution of single microwave frequency radiation. The more uniformfield distribution of VFM produces fewer hot spots, resulting in moreuniform heating of the composite. Moreover, generally, no singlefrequency is applied for longer than about 25 μsr, or no longer thanabout 20 μs, or no longer than about 15 μs, or even no longer than about10 μs. The short duration of each applied frequency produces no build-upof charge, thus eliminating discharge, or arcing, typically observedduring single frequency microwave irradiation.

In certain embodiments, the range of microwave radiation frequencies isin the range of from about 7.9 GHz to about 12.0 GHz. In still others,the range of microwave radiation frequencies is in the range of fromabout 7.9 GHz and 8.7 GHz. In some embodiments, range of microwaveradiation frequencies is in the C-Band frequency range, the C-Bandfrequency range encompassing microwave frequencies in the range of fromabout 4.0 GHz to about 8.0 GHz. In other embodiments, the range ofmicrowave radiation frequencies is in the X-Band frequency range, theX-band frequency range encompassing microwave frequencies in the rangeof from about 8.0 GHz to about 12.0 GHz.

Preferably, the sweeping of the range of microwave radiation frequenciesencompasses one or more pre-selected microwave radiation frequencies inthe range of from about 4.0 GHz to about 12.0 GHz. This frequency can beselected by using the methods described herein and techniques known inthe art. In one embodiment, the pre-selected microwave radiationfrequency is in the range of from about 7.9 and about 8.7 GHz. In otherembodiments, the bandwidth of the sweeping range of microwave radiationis about 4.0 GHz. More preferably, the range of microwave frequencieswith which the composition is swept, is about +/−2 GHz of thepre-selected microwave radiation frequency. For example, if thepre-selected microwave radiation frequency is 7.2 GHz, the compositionwould be swept with the range of microwave radiation frequenciesencompassing from about 5.2 to about 9.2 GHz.

Upon extraction, flammable hydrocarbon-based gases are released. Toreduce the risk of ignition, it is preferred that the method beperformed in an oxygen-deprived atmosphere. Preferably, the composite isexposed to less than about 12% oxygen. More preferably, the composite isexposed to less than about 8% oxygen. Even more preferably, thecomposite is exposed to less than about 5% oxygen.

In one embodiment, the composite is exposed to an inert gas atmosphere.Preferably, the inert gas is nitrogen, argon, or mixtures thereof.

In some embodiments, the composite is exposed to less than atmosphericpressure. Preferably, the composite is exposed to less than about 40Torr. More preferably, the composite is exposed to less than about 20Torr. Even more preferably, the composite is exposed to less than about5 Torr.

In one embodiment, the composite is subjected to microwave radiationsufficient to heat the petroleum-based material to its boiling pointtemperature. Boiling point temperatures of petroleum-based materials areknown in the art. Reducing the pressure at which the composite isexposed will result in a decrease in the boiling point temperature ofthe petroleum-based material. Those of skill in the art will be able todetermine the boiling point temperatures of petroleum-based materials atdifferent pressures.

In some embodiments, the methods of the present invention may be used insitu to extract petroleum-based materials from composites located in thefield. In other embodiments, inert gases may be flowed, in situ, ontothe composites. In one embodiment, the pressure surrounding thecomposite may be reduced to below atmospheric pressure.

Using the methods of the present invention, oil and/or gases can berecovered from the composite.

The petroleum-based material extracted using the methods of the presentinvention may be refined and/or purified using techniques known in theart.

The present invention also provides for apparatuses for decomposing acomposition comprising a petroleum-based material. In one embodiment,the apparatuses of the present invention comprise a microwave radiationgenerator, wherein the generator is capable of applying microwaveradiation characterized as having at least one frequency component inthe range of from about 4.0 and about 12.0 GHz, and at least onecontainer to collect decomposed components from the composition. In oneembodiment, the microwave radiation generator is capable of applying amicrowave radiation frequency between about 4.0 and about 12.0 GHz.

In other embodiments, the apparatuses of the present invention comprisea microwave radiation generator, wherein the generator is capable ofapplying a sweeping range of frequencies of microwave radiationcharacterized as having at least one frequency component in the range offrom about 4.0 GHz to about 12.0 GHz, and at least one container tocollect decomposed components from the composition. In otherembodiments, microwave radiation generator is capable of applyingsweeping microwave radiation in the C-Band frequency range. In yet otherembodiments, microwave radiation generator is capable of applyingsweeping microwave radiation in the X-Band frequency range. In yet otherembodiments, microwave radiation generator is capable of applyingsweeping microwave radiation in the Ku-Band frequency range (about 12GHz to about 18 GHz). In further embodiments, the microwave radiationgenerator is capable of applying sweeping microwave radiation in therange of about 5.8 GHz to about 7.0 GHz. In yet other embodiments, themicrowave radiation generator is capable of applying sweeping microwaveradiation in the range of about 7.9 GHz to about 8.7 GHz.

In another embodiment, the chamber is open to the outside atmosphericconditions. In other embodiments, the chamber is closed to the outsideatmosphere. In yet other embodiments, the chamber has an internalpressure of less than atmospheric pressure. Preferably, the chamber iscapable of operating at a pressure of less than about 40 Torr. Morepreferably, the chamber is capable of operating at a pressure of lessthan about 20 Torr. Even more preferably, the chamber is capable ofoperating a pressure of less than about 5 Torr.

The present invention also provides for apparatuses for extracting apetroleum-based material from a composite comprising the petroleum-basedmaterial. In one embodiment, the apparatuses of the present inventioncomprise a microwave radiation generator, wherein the generator iscapable of applying microwave radiation characterized as having at leastone frequency component in the range of from about 4.0 GHz to about 12.0GHz, and at least one container to collect the extracted petroleum-basedmaterial. In some embodiments, the microwave radiation generator iscapable of applying a microwave radiation frequency of characterized ashaving at least one frequency component in the range of from about 4.0and about 12.0 GHz.

In other embodiments, the apparatuses of the present invention comprisea microwave radiation generator, wherein the generator is capable ofapplying a sweeping range of frequencies of microwave radiationcharacterized as having at least one frequency component in the range offrom about 4.0 GHz to about 12.0 GHz, and at least one container tocollect the extracted petroleum-based material. In some embodiments, themicrowave radiation generator is capable of applying sweeping microwaveradiation in the C-Band frequency range. In yet other embodiments,microwave radiation generator is capable of applying sweeping microwaveradiation in the X-Band frequency range. In further embodiments, themicrowave radiation generator is capable of applying sweeping microwaveradiation in the range of about 5.8 GHz to about 7.0 GHz. In yet otherembodiments, the microwave radiation generator is capable of applyingsweeping microwave radiation in the range of about 7.9 GHz to about 8.7GHz.

In some embodiments, the apparatuses of the present invention may beused in situ to extracted petroleum-based materials from compositeslocated in the field.

In other embodiments, the apparatuses further comprise at least onechamber for holding the composite. In another embodiment, the chamber isopen to the outside atmospheric conditions. In other embodiments, thechamber is closed to the outside atmosphere. In yet other embodiments,the chamber has an internal pressure of less than atmospheric pressure.Preferably, the chamber is capable of operating at a pressure of lessthan about 40 Torr. More preferably, the chamber is capable of operatingat a pressure of less than about 20 Torr. Even more preferably, thechamber is capable of operating at a pressure of less than about 5 Torr.

In other embodiments, the apparatuses further comprise at least onechamber for holding the composition. The volume of the compositions ofthe present invention may reduce during decomposition. In someembodiments, the chamber may have a conveyor having a perforated bottomsuch that decomposed materials may fall out of the chamber once reachinga particular size, so as not to over-expose the materials to microwaveradiation. The conveyor may be adapted to be oscillated.

An exemplary embodiment of the present invention is depicted in FIGS.1A-1G. FIGS. 1A-1G demonstrates one apparatus wherein tire fragments areplaced on a first conveyor belt that carries the tire pieces throughthree, differently-sized chambers of the apparatus. In a first chamber,the tire pieces are exposed to microwave radiation using the methodsdescribed herein. As the tire fragments decompose, the smaller pieceswill fall through perforations in the first conveyor and drop to asecond conveyor. The second conveyor is not exposed to microwaveradiation in the first chamber. The second conveyor carries the piecesto a second chamber, wherein they are exposed to microwave radiationusing the methods described herein. As the pieces decompose, the smallerpieces fall through the perforations in the second conveyor to a thirdconveyor. The perforations in the second conveyor are smaller than theperforations in the first conveyor. The third conveyor is not exposed tomicrowave radiation in the second chamber. The third conveyor carriesthe pieces to a third chamber, wherein they are exposed to microwaveradiation using the methods described herein. As the pieces decompose,the smaller pieces fall through the perforations in the third conveyorto a fourth conveyor. The perforations in the third conveyor are smallerthan the perforations in the second conveyor. Decomposition will beessentially complete after exposure in the third chamber and thematerial remaining on the fourth conveyor will be mainly steel, carbonblack, and ash, which can be further processed using techniques known inthe art.

FIG. 1 comprises FIGS. 1A-1F, along with inset FIG. 1G. The orientationof FIGS. 1A through FIG. 1F are set forth in the inset in FIG. 1.Referring to FIGS. 1A-1G, there is provided an embodiment of the presentinvention directed to processing tire cuttings using microwaves torecover fuel oil. The processing equipment described herein iscommercially available from one or more process equipment manufacturingcompanies.

FIG. 1A illustrates an elevation view of the beginning section of a tirecuttings plant layout according to an aspect of the present invention.This illustration shows two tire processing lines side-by-side in aparallel configuration. Tires from automobiles and trucks are first cutinto suitable chips, e.g., 4×4 or 5×5 chips (not shown). The tire chipsare transported using incline belt conveyor 120 to accumulation silos102. The tire chips are then conveyed from the accumulation silos 102 toa pre-washer screw wash section 122. Tire chips are then conveyed to apressure washer hot water sonic washer 105. Dirt, stones, gravel andother debris is cleaned off of the tire chips to minimize contaminationof the process further downstream. The tire chips are then dried usingforced air dryer system 106. FIG. 1B is a plan view of the beginningsection of a tire cuttings plant layout corresponding to FIG. 1A.Cleaned and dried tire chips are then conveyed up another conveyor 120,as set forth in FIGS. 1C and 1D, below.

FIG. 1C is an elevation view of the midsection of the tire cuttingsplant layout described here. Cleaned and dried chips are transported toaccumulation silo 112, which are then transported along transportconveyor 120 to microwave room 124. The details of the microwave room124 or further described in FIG. 1G below. In this elevation view, adual wall tank with enclosed high high-capacity heat exchanger 118 isshown in dotted lines. This high-capacity heat exchanger receiveshydrocarbon vapor produced by the microwave reactors residing within themicrowave room 124. The position of the dual wall tank with enclosedhigh-capacity heat exchanger 118 is illustrated further in FIG. 1D.

FIG. 1D is a plan view of the midsection of the tire cuttings plantlayout described here. Accumulation silos 112 feed tire chips viaincline belt conveyor 120 and screw feed in-feed section 117 to a seriesof microwave reactors within hermetically sealed reactor room 116 withfiltration system and vacuum pumps. Tire chips in the screw feed in-feedsection 117 are fed into a first microwave reactor 150 (see FIG. 1G)residing within the microwave room 116. The microwave room is depictedin FIG. 1D containing two sets of microwave reactors side-by-side.Additional microwave reactors and additional lines can also be added.Hydrocarbon vapors generated in the microwave reactors from theirradiated tire chips are collected out of the top of each of themicrowave reactors. The hydrocarbon vapors are then transported, undervacuum (e.g. at a pressure less than ambient) to heat exchanger 118. Theheat exchanger is capable of further separating hydrocarbon vapors tooil and high carbon gases by cooling to a liquid or a vapor, dependingon the vaporization temperature of the hydrocarbon vapors.

The microwave reactor room 116 is also depicted having refrigerationequipment 123 for maintaining constant room temperature. Processed tirechips exit the microwave reactor 154 (FIG. 1G) by a screw feed dischargesection 115. Processed tire chips exit the final microwave room hot andare subsequently cooled using cooler 114. The cooled processed tirechips (below about 110° F.) then enter a pregrader grinder system 113,where processed carbon containing materials are separated from metallicmaterials (e.g., metal tire cords). Metal materials are separated usinga suitable magnetic conveyor take away system, as shown in 121 in FIGS.1E and 1F. Organic particles (e.g. carbon black) can further be shippedto bulk feed trucks equipped to handle fine particles, other packaging,as well as rail cars. The resulting organic particles are composedprimarily of carbon. In some embodiments, the organic particles can beused as electronic activators, as described herein.

FIGS. 1E and 1F illustrate the magnetic conveyor take away system 121for separating metal particles from nonmagnetic organic matter. Metal isstored in a metal storage unit 140 while nonmagnetic organic matter(e.g., carbon particles) is transported via incline belt conveyor 120 tosilo and grinder 130. Carbon particles prepared according to theprocesses of the present invention are suitable for use as electronactivators for the microwave processing of heavy residual refinery oiland other materials (e.g., residual oil from the bottom of a hydrocarbondistillation apparatus that is traditionally unable to be furtherprocessed). In one embodiment, the tire sidewalls can be separated fromthe tire treads. Tire treads typically have a greater amount of carbonblack than the sidewalls. Accordingly, the amount of carbon blackrecovered from the treads is greater than that of the sidewalls. In oneaspect, carbon black can be accumulated to form electron activator byprocessing the treads. Electron activator that can be further used inprocessing heavy viscous oil feedstocks. Also present is a sifter systemwith grinder return 111 for preparing controlled particle size carbonmaterial. The matter in the silo and grinder 130 is transported by apneumatic tube conveyor system 119 and auxiliary pump 136 toward sifter132, and then to sorter 134, and finally to a super sack gantry system138. The super sack entry system 109 is suitable for loading andunloading using forklift delivery. Also shown is electrical enclosure108 containing control panels, a centrifugal feeder/sorter system 110for managing fine particles.

As shown in FIGS. 1D and 1G, the microwave reactor room contains twoseries of three reactors each (one series is illustrated in FIG. 1G).Tire pieces enter first reactor 150 via screw feed infeed section 117.This reactor is the largest reactor of the series. 4×4 or 5×5 inch tirechips are first exposed to microwaves in the first reactor 150 byoperation of the microwave antennas in the first microwave chamber 161.In this first stage, the tire pieces “pop” or explode into smallerpieces when exposed to the microwaves. The smaller pieces are separatedthrough a mesh belt 170, and then transported onto anothertransportation mesh belt 172. The mesh is designed to keep themicrowaves in the first reactor from getting through and over heatingthe tire chips. Typically, the temperature of the tire chips ismaintained at about 465° F. or less. The mesh size in the larger reactorwill have an opening of approximately 2 inches, the mesh size in themidsized reactor is approximately 0.5 inches, and the mesh size openingfor the smallest reactor is approximately 1/16″.

Microwaves are generally generated outside of the microwave room andtransported into the microwave room by a suitable microwave conduit,e.g. stainless steel wire. The design and interconnection of the threemicrowave reactors in series is provided so that the location of thetire chips in the microwave radiation zone is maintained so that thetire chips do not exceed 465° F. Initially, “popping” of the tire beginsin the first reactor 150 when the temperature of the tire chips is inthe range of from about 300° F. to about 450° F. It has beensurprisingly found that once the temperature exceeds about 450° F., thecarbon black residing within the tires can be charred and overcooked andthe efficiency of the process for recovering hydrocarbon fuel oilsdiminishes drastically. Accordingly temperature is desirably maintainedbelow about 465° F., or even below about 550° F. Without being bound byany particular theory of operation, it appears that the tire chips popbecause the reactors are under vacuum and a lot of gas within the tirechips is being released suddenly upon irradiation with microwaves.

Suitable operating pressures are the range of up to about 20 mm ofmercury, or even up to about 40 mm of mercury, or even up to about 100mm of mercury. Accordingly, tire chips processed in the first microwavereactor 150 are then transported to the second microwave reactor 152,where the processed chips are further irradiated under vacuum usingmicrowave antennas 162. The tire chips are further reduced in size, andfall through mesh 174, and then transported to the third microwavereactor 154. In the third microwave reactor 154, the processed chips arefurther irradiated using microwave antenna 164. Processed chips arefinally transported by a screw feed discharge section 118 and exit themicrowave reactors from screw feed discharge section 166, and throughairlock (not shown) and onto conveyor 156.

Each of the microwave reactors are fed with microwave conduitsterminating in a suitable cone or nozzle. The first microwave reactorhas more microwave nozzles 160 as it is larger than the other twomicrowave reactors. The second microwave reactor is shown with microwavenozzles 162, and the third microwave reactor is shown with microwavenozzles 164. Each of the microwave reactors contains vacuum lines 180 totransport the resulting hydrocarbon gases to the high-capacity heatexchanger 118 (shown in dotted lines). Also shown in the microwave room124 are refrigeration equipment 123 to maintain the temperature of theambient conditions in the microwave room, and support structures 158 forsupporting the microwave reactors.

Suitable microwave ranges for the processing of tire chips includesusing X-band microwave radiation generators (not shown) transmitted viaconduit in tubes at various frequencies to each of the reactors.Microwave frequencies for tire processing varies from X-band downtowards C-Band radiation. X-band is 5.2 to 10.9 GHz; C-band is 3.9 to6.2 GHz. K-band radiation is also useful in some embodiments. K-band is10.9 GHz to 35 GHz, which includes the sub-bands Ku (15.35 GHz to 17.25GHz) and Ka (33.0 GHz to 36.0 GHz). Typically separate microwave antennatubes are separated in frequency by approximately 0.2 gigahertz. In theembodiment shown in FIG. 1G, a total of approximately 36 microwaveantenna tubes are transported from a microwave source (not shown) to themicrowave reactors. The largest microwave reactor 150 has the greatestnumber of tubes, for example about 18. The second microwave reactor 152has fewer tubes, approximately 12. The third microwave reactor 154 hasthe fewest number of tubes, approximately 60. Each of the tubes arecapable of operating at different frequencies, which frequencies incertain preferred embodiments varies between about 7.0 and 6.4 GHz. Theends of the microwave antenna from which the microwave radiation exitsinto the reactor chambers are fitted with a suitable cone antenna. Eachof the cone antennae emits microwave radiation at a separate frequency,which is typically about 0.2 GHz different than the others thatirradiate into each of the microwave reactors. Microwaves are typicallyfixed in frequency but they may also be capable of being swept in avarying frequency manner, for example, by using a variable frequencymicrowave generator. A number of different frequency combinations areenvisioned, for example each of the cone antennas may be fixed infrequency, vary in frequency, or any combination thereof. As the tirechips are irradiated, volatile hydrocarbon vapors are emitted from thetire chips and collected by vacuum tubing. Hydrocarbon vapors are thentransported to a heat exchanger condenser. Highly volatile gases andvapors that are not conveniently liquefied can be separately recoveredas a high BTU gas product.

The plant layout described in FIGS. 1A-1G is operated at a product speed(per line) of approximately 30 tires per minute on average. Hourlyproduction rate is approximately 36000 pounds per hour or approximately1300 ft.³ per hour. This is based upon a used automobile tire weight ofapproximately 20 pounds (9.1 kg). Or alternatively a used truck tireabout 40 pounds (18.2 kg). The shredded tire chip sizes can be in therange of from about 3 to about 5 inches. Average loose density of thechips is approximately 24 pounds per cubic foot to about 33 pounds percubic foot. Heat values generated at atmospheric pressure range fromapproximately 12,000 BTUs per pound to about 15,000 BTUs per pound.

FIG. 2A is an elevation view, axial direction, of a microwave reactorsuitable for processing oil cuttings according to an aspect of thepresent invention. Oil cuttings comprise dirt, rock, water, carbondeposits, and the like, which oil cuttings are obtained during drillingoperations. Drilling operations include drilling from an oil rig,drilling from a deep-sea oil platform, as well as mining of shale rockand coal deposits. During drilling, rock that is rich in hydrocarbons istypically reached prior to hitting a pocket of oil. This hydrocarbonrich rock is transported up to the surface and can comprise up to 15%oil, and even up to 25% oil. The consistency can also be similar to oilshale. Hydrocarbon rich rock can be considered hazardous waste and wouldneed to be disposed of properly. It cannot be sent to a landfill, andaccordingly it has traditionally been handled by combustion. This isparticularly a problem on an oil rig in the middle of the ocean, whereit may be forbidden to dump oil drillings comprising greater than 1%hydrocarbon content. Accordingly, the process of the present inventioncan also be used to recover hydrocarbons from drill cuttings, therebypermitting the drill cuttings to be placed back in the environment afterthe hydrocarbons have been substantially removed. As used herein theterm “substantially removed” refers to a composition comprising lessthan 1% by weight hydrocarbon content. Oil drill cuttings having lessthan 0.01% by weight hydrocarbon has been produced using the processesdescribed herein. Accordingly, the methods suitably provide drillcuttings that comprise less than 1 percent, or even less than 0.5percent, or even less than 0.2 percent, or even less than 0.1 percent,or even less than 0.05 percent, or even less than 0.02 percent, or evenless than 0.01 percent by weight hydrocarbons based on weight oilcuttings. Suitable oil cuttings enter into the system through in-feedgrinder system 201. Oil cuttings are ground to a suitable size, then fedinto the microwave reactor chamber (vacuum sealed reactor tank 216) viain feed screw 202. The vacuum sealed reactor tank 216 contains a helicalmixer element 203 for mixing and stirring the ground oil cuttings. Thereactor tank is typically filled to about 40% of its total volume. Themicrowaves irradiate the contents of the reactor via antennas that areoriented in an orbital arrangement emanating from the top of thereactor. The microwave antennas are desirably flexible and irradiatefrom several slides from the top the reactor towards the mixing materialbelow. A helical mixer element is turned using a motor 210. Microwavesemanating from a cone antenna or a plurality of cone antennas (notshown) irradiate the oil cuttings with suitable microwave radiation.Hydrocarbon gases and oil vapor exit towards the top vacuum tubingtowards vacuum pump and collected in a suitable heat exchanger vaporcondensing unit. Hydrocarbon vapor gases produced by the process ofirradiating the oil cuttings with microwaves exit via a vacuum dischargetube (not shown). Residual geologic material and unreacted carbondeposits settled towards the bottom of the reactor. The unvaporizedmatter is discharged from the microwave reactor 216 via screw feeddischarge section 204, and exits the system via discharge system 206.Material exiting the system is suitably clean of hydrocarbons so as tobe considered nonhazardous waste. For example, material exiting thereactor can be returned to the ocean after drilling, or can be returnedto the land after drilling. Also shown is reactor support structure 205for holding the components as set forth in the system.

FIG. 2B illustrates an elevation view of the microwave reactor of FIG.2A, longitudinal direction. Oil cuttings are added to the system asin-feed via an airlock at 201, which oil cuttings are then transportedto the reactor 216 via in-feed screw 202. Depicted in this diagram isconduit 214 for pulling vacuum on the airlock, and on the vacuum sealedreactor tank 216, using vacuum pumps 207. Microwave waveguides 212 areshown entering the vacuum sealed reactor tank 216. Microwaves emanatingfrom a suitable microwave cone antenna radiates the oil cuttings withinthe reactor tank. A helical mixer element 203 rotates to mix the oilcuttings, convey the oil cuttings, and reflects microwaves throughoutthe volume of the chamber. After suitable microwave processing at aparticular residence time, the reacted oil cuttings exits the reactorthrough screw feed discharge section 204 and exits via a suitableairlock 206 of the discharge system. Also shown is reactor supportstructure 205.

FIG. 2C illustrates an elevation view of the microwave device andcontrol room suitable for generating microwaves and propagating the samethrough waveguides. The microwave device and control room 208 isdepicted as comprising an electrical panel and a series of sixindividual microwave generators (222, 226, 230, 234, 238, and 242) eachconnected to a series of microwave antennas (220, 224, 228, 232, 236,and 240). The antennas are combined into a combined antenna conduit 212which exits the microwave device control room 208 and leads towards thevacuum sealed reactor tank 216 as shown in FIG. 2B. Suitable microwavesfor processing oil drill cuttings have frequencies in the range of about11.2 to about 11.8 GHz, typically about 11.5 GHz. Oil shale can also beprocessed using the equipment and processes described herein at amicrowave frequency in the range of from about 10.6 to about 11.2 GHz,and typically about 10.9 GHz. Tar sands can be appropriately processedusing microwaves 4 to about 12 GHz. Tar sands can also be processed inthe K-band, preferably in the Ku band. Anthracite coal deposits can alsobe processed in the KU band as well. A vacuum is maintained within themicrowave reactor chamber using suitable vacuum and hydrocarbon vaporcondensation equipment, for example at pressures less than about 100 mmof mercury, and even at pressures of less than about 40 mm of mercury,or even at pressures of less than about 20 mm of mercury. Maintainingsuch low operating pressures helps to keep the overall processtemperatures below about 465° F. or even a temperatures less than about450° F. so as to prevent overheating and efficient recovery ofhydrocarbon vapors. A large proportion of the hydrocarbon vapors can becondensed into liquid fuel oil at ambient temperatures.

The system described in FIGS. 2A-2C can be suitably adapted and scaledto process oil cuttings at a throughput of up to about 2 tons per hourto even up to about 10 tons per hour. It should be readily apparent tothe skilled person how to increase the size and power of the microwavereactor chamber to yield higher throughputs.

The system described in FIGS. 2A-2C can also be suitably adapted inscale to process oil shale rock. The processing of oil shale rockincludes irradiating it with suitable microwaves at power sufficient toincrease the temperature of the oil shale rock to within a range of fromabout 500° C. to about 600° C. Without being bound by any theory ofoperation, it is believed that these processing temperatures areconsiderably hotter than compared to tire cuttings for the reason thatmore energy needs to be applied to the rocks to volatile lies thehydrocarbons. This is in contrast to softer, substantially higherconcentration hydrocarbon, tires that readily absorb the microwaveenergy. Suitable shale rocks are broken down into small pieces afterbeing mined For example, shale rock pieces are suitably smaller than aninch cube, even smaller than a half inch cube, or even smaller thanabout ⅜″ cube, even smaller than about a half inch cube, or even smallerthan about ¼″ cube. The hydrocarbon content of the oil shale rocktypically comprises hydrocarbons comprising from about C10 to about C25,or even from about C14 to about C22. Oil shale rock can contain up toabout 5% by weight hydrocarbons, or even up to about 15% by weighthydrocarbons, or even up to about 25% by weight hydrocarbons. In somecases, shale rock can contain up to about 70% by weight hydrocarbons.

FIGS. 3A and 3B depicts several embodiments of the present invention forrecovering petroleum-based materials and hydrocarbons from oil slurry.FIGS. 3A and 3B are schematic illustrations of two embodiments of amicrowave assisted system for the distillation and recovery of heavy oilbottoms, e.g., oil slurry, from a distillation plant. FIG. 3A shows thefollowing elements of a traditional hydrocarbon distillation plant: 302distillation tower 360 unrefined inlet into distillation tower; 304vapor line; 306 natural gas line; 308 gas separator; 310 pump; 312 LPGline; 314 gasoline lines; 316 jet fuel (kerosene) line; and 318 inset:close-up view of the liquid vapor contact caps with an a distillationtower. This distillation system can be modified using the microwaveprocess of the present invention as follows. An electron activator 320is added using an electron activator pump 322 into residual oil 362. Hotresidual oil line (e.g., heavy oil) 362 is pumped into the microwavereactor 330 and atomized using an atomizer 334. Microwave waveguideantenna 336 is powered from the microwave room and control system 340,which control system includes microwave generators 342 and microwavewaveguides 344. The microwaves exit the waveguide antenna 336 at conenozzles within the microwave reactor so as to radiate the atomizedresidual oil above the atomizer 334. Vacuum pumps 350 connected to thevacuum line 332 maintains pressure of less than about 20 mmHg, or evenless than about 40 mmHg, or even less than about 100 mmHg Theirradiation of the atomized residual oil gives rise to cracking of theresidual heavy oil, which in turn produces hydrocarbon vapors such asnatural gas 352 and heavier hydrocarbon vapors such as diesel andheating oil 354. In the microwave reactor 330, residual oil 362 isremoved from the bottom of a distillation tower 302, combined withelectron activator 320 and processed by microwave after atomization. Wehave discovered that addition of the electron activator to the residualoil, for example about 2% by weight based on residual oil of carbonsmall particles, gives rise to a much faster, more efficient absorptionof the microwaves to yield more efficient cracking of the residual oil.Accordingly, electron activator made using microwave processing of tirechips as described supra is useful for making electron activator.Suitable electron activator is provided as a fine powder, for example ofabout a hundred mesh, or finer. The electron activator may be coarserthan 100 mesh, depending on the precise application and handlingrequirements. Without being limited by any particular theory ofoperation, the electron activator enhances the absorption of microwavesby the residual oil, which gives rise to faster processing and moreefficient processing of the heavy oil. As a result, the electronactivator, which comprises carbon powder particulates, are capable ofabsorbing microwave radiation. Solid particles containing residualhydrocarbons, such as electron activator, result in popping (as inpopcorn) when irradiated. Without being bound by any particular theoryof operation, it is believed that the popping action of the smallelectron activator particles within the residual oil enhances themicrowave processing of the residual oil. In certain embodiments, theelectron activator functions as a catalyst for effectuating themicrowave cracking process.

Suitable microwave radiation frequency ranges from about 8.0 to about8.8 GHz, or in the range of from about 8.1 GHz to about 8.7 GHz, or evenin the range of from about 8.2 GHz to about 8.6 GHz, or even in therange of from about 8.3 GHz to about 8.5 GHz, or even about 8.4 GHz. Themicrowave reactor contains a series of microwave cone antennas thatradiate the atomized residual oil with microwaves. These microwave coneantennas can each receive the same or different microwave frequencies.When the frequencies differ, they typically are separated by incrementsof about 0.2 GHz. Ranges of microwave frequencies are typically usefulfor processing the atomized residual oil in this manner. Accordinglymultiple microwave antennas 344 receive microwaves generated by aplurality of microwave generators 342 provided in the microwave controlsystem 340. Microwaves are transmitted through microwave antennas 344 tothe microwave antenna conduit 336. Microwaves then enters the microwavereactor. Typically the residual oil 362 is pre-heated to a temperatureof about 350° C. so that it is capable of flowing under pressure andatomized. The use of microwaves has been demonstrated to effectivelycrack the hydrocarbon chains in the heavy residual oil. Atomizationhelps to increase the surface area of the residual oil and decreaseparticle size, thereby effectuating absorption of the microwaves andcracking of the hydrocarbon chains. The residual oil is suitably heatedto temperatures sufficient that can flow under pressure and atomized.Suitable temperatures are at least about 250° C., or even at least about300° C., or even at least about 350° C., or even at least about 400° C.,or even at least about 450° C., or even at least about 500° C. Theresidual oil may be preheated using any of a variety of heating methods,for example convection, conduction, or irradiation, e.g. microwaves. Theheavy residual oil chains crack at least several times.

Processes according to the present invention are capable of producingcombustible gases. The processes according to the present invention arealso capable of producing at least several different weights of oils.These oil products range from carbon content of hydrocarbon chainscomprising from 14 carbons up to about 25 carbons. The starting residualoils comprise hydrocarbon chains having at least 25 carbons or even atleast 28 carbons. The hydrocarbons in the residual oil do notnecessarily need to be linear hydrocarbon chains, for example cyclic andbranched hydrocarbons are also envisioned. Instead of atomization, hotflowing residual oil can be formed into a thin film and irradiated withmicrowaves, or can be ejected into a shooting stream and irradiated withmicrowaves, or can be broken into droplets under force of pressure andirradiated with microwaves. Similar related processes give rise tonarrow dimension residual oil droplets. In certain embodiments theproducts of microwave radiation within the microwave reactor 330illustrated in FIG. 3A can be recycled back to the distillation tower302 for further processing.

FIG. 3B is a schematic of another embodiment of a microwave assisteddistillation and recovery unit for heavy oil bottoms from a distillationplant. This embodiment is similar to that described in FIG. 3B, with theexception that this embodiment further includes a reboiler 348 forheating the bottoms coming from distillation tower 302 by a transferline 370. The reboiler heats the bottoms which are distilled in vacuumtower 340. Residual oil 346 from the vacuum tower is combined withelectron activator 320 using electron activator pump 322 to provide amixture of residual oil in electron activator 362. This mixture is thenatomized in microwave reactor in 330. The operation of the microwavereactor is similar to that discussed supra in FIG. 3A.

FIG. 4A illustrates an elevation view of a microwave reactor systemsuitable for processing shale rock, tar sands, drill cuttings, and thelike. Inlet feed screw 402 is suitable for transporting shale rock andother hydrocarbon containing cuttings and the like into microwavereaction chamber 412. Helical screw mixing flights 408 are mounted to anaxle 406 which is rotated using a motor. Helical screw mixing flightsmix and transport the material, such as shale rock pieces, in themicrowave reaction chamber interior 404. Microwave antennas 410 enterthe interior of the microwave reaction chamber 404. The material withinthe microwave reaction chamber interior is stirred and irradiated.Vapors are removed using a vacuum recovery system and condensing unit(not shown). Material depleted of hydrocarbon vapor is dischargedthrough the exit discharged from feed system 416. Also shown is asupport structure 414.

FIG. 4B provides a plan view of FIG. 4A, wherein the direction of thematerial is shown entering the microwave reaction chamber via onlet feedscrew 402 mixing within the microwave reaction chamber by a helicalscrew mixing flights 408, and finally exiting via exit discharge screwfeed system 416. FIG. 4C is an elevation view of the microwave reactorsystem along the axis 406, the near end being the exit discharge screwfeed system section 416. FIG. 4D illustrates a suitable microwave devicecontrol room, waveguides, and vacuum pumps suitable for use with thesystem illustrated in FIG. 4A. FIG. 4E illustrates an optional hopperelevator for transporting material into the inlet feed section 402.FIGS. 4F and 4G illustrate three horizontal microwave reactor systemsoperating in parallel. FIG. 4H illustrates additional microwavegenerators, waveguides and vacuum pumps for operating the threehorizontal microwave reactors illustrated in FIGS. 4F and 4G. Theprocessing of hydrocarbon containing materials, such as shale rock, tarsands, drill cuttings and the like, is conducted in a vacuumenvironment, less than about 20 mm of mercury, or less than about 40 mmof mercury, or even about less than 100 mm of mercury. The hydrocarboncontaining materials are subject to heating by the microwaves and otherheating means, up to about 350° C., or even up to about 450° C., or evenup to about 550° C., or even up to about 600° C. The hydrocarboncontaining materials are removed from the microwave reactor chamber viaa suitable vacuum plumbing system. The hydrocarbons are recovered usinga suitable heat exchange or condensing system (not shown).

FIG. 5A depicts an exemplary embodiment of the present invention forextracting petroleum-based materials, carbon-based materials andhydrocarbon-based materials in situ. A probe capable of generatingmicrowave radiation (e.g., cone, antennae or nozzle) according to themethods of the present invention can be lowered into drilled oil wells.Using the methods of the present invention, the petroleum-basedmaterials can be vaporized and collected at surface-level and processedusing techniques known in the art. FIG. 5A illustrates a schematic viewof a microwave system for in situ recovery of oil from geologicdeposits. A suitable geologic deposit 526 includes an oil well, a cappedoil well, a shale rock deposit, a tar sand deposit, a coal deposit, andthe like. This illustration depicts a vacuum recovery unit 502 (e.g., aVenturi type system) for recovering geologic hydrocarbons such as fossilfuels from a capped oil well. This system comprises casing 504 extendingfrom the surface of the ground to the geologic carbon deposits at 526. Amicrowave waveguide is delivered through the casing to the geologiccarbon deposit 526. A microwave antenna nozzle 510 resides at the end ofthe microwave waveguide 506 proximate to the geologic carbon deposit,into which microwaves radiate. On the ground surface is illustratedportable electric generator 522, portable pumping system 524, andportable microwave generation station control unit 520. Hydrocarbonvapors generated by the microwaves in the geologic carbon deposit 526are transported under vacuum as vaporized geologic carbon deposit (e.g.,oil vapor) 508 to the vacuum recovery unit on the surface ground. Cappedoil wells contain hydrocarbons that can be cracked to oil, suitable foruse as diesel fuel. This involves opening up capped oil wells,optionally adding electron activator into the wells (which aid inabsorbing the microwaves and converting the heavy oil in the wells tohydrocarbon vapor), and irradiating the heavy hydrocarbons withmicrowaves. Once vaporized, the hydrocarbons are readily transported tothe surface using suitable vacuum piping, or other plumbing means 528.The vacuum recovery unit 502 is also capable of fractionating thehydrocarbons into other hydrocarbon products. Oils that are difficult torecover using normal pumping means can be recovered according to theprocesses.

FIG. 5B depicts an apparatus of the present invention for recoveringpetroleum-based materials from oil shale, in situ. A probe capable ofgenerating microwave radiation according to the methods of the presentinvention, can be lowered into oil shale deposits. Using the methods ofthe present invention, the petroleum-based materials can be vaporizedand collected at surface level and processed using techniques known inthe art. FIG. 5B illustrates a schematic view of a microwave system forrecovering hydrocarbons below ground. In this embodiment, one or moremicrowave antennae are shown capable of traveling horizontallyunderground with respect to the ground surface. The microwave antennaeare illustrated comprising one or more microwave nozzles for vaporizinghydrocarbon geological deposits in a vacuum environment. FIG. 5Billustrates two conduits (on the left portion of the figure), eachcontaining a plurality of waveguides that terminate it into a suitablemicrowave nozzle or cone emitter. Suitable microwave cones emitters arecommercially available. This process is adapted for recovering residualoil in capped oil wells, and can also be adapted to other geologicalhydrocarbon deposits such as tar sands and shale rock. If the oil wellis “dry” with mainly heavy viscous hydrocarbon material remaining in thewell, a microwave antenna is transported down into the oil well and theantenna-end can reside in one or more of the openings. Microwaveradiation is directed towards the geologic material in the vicinity ofthe antenna.

Various hydrocarbon geological deposits can be processed undergroundusing this technology at various depths. Piping for the wells can startat a diameter of about 24 inches at the surface, which diameter isprogressively narrower and narrower as sections of piping are added asthe depth increases. At a depth of approximately 3000 feet, a typicalopening (diameter) of the piping is about 6 inches. For example oilshale deposits in the Western part of the United States are relativelyshallow, i.e., near the surface. Strip mines are also relativelyshallow, and other deposits may be as deep as 2000 feet or more.Previously pumped oil wells often have chambers of oil that are notreadily accessible but require opening by an additional explosive ordrilling operation. Certain chambers can also be opened by irradiatingthe sealing rock material with microwaves. In a laboratory setting, ithas been discovered that oil shale pops and reduces in size whenirradiated with microwaves. As the oil shale releases hydrocarbons (i.e.oil), the oil shale “pops” like popcorn. Accordingly, directionalizingmicrowaves within the geological chambers can give rise to breakdown ofthe geological formation (i.e. the rocks pop, break apart, and fall downand fill the cavity). Accordingly, the antennas can be moved aroundwithin geological formations to aid in recovering hydrocarbon material.In some embodiments microwave antennas are placed down about 5000 feetor more, and then are directionalized to travel on the order ofapproximately 100 yards or so horizontally.

Any type of hydrocarbon material present within the geological formationcan be cracked to gas and recovered at the surface usingfractionalization condensation units. For example, any carbon suitablefor use as diesel fuel can be made by irradiating oil shale. Resultingdiesel fuel is suitably used as Cat Diesel Engine Oil. Sometimes oilwells are drilled using directional drilling technologies. Suitabledirectional drilling technologies are capable of bending at a rate of adegree a foot to create an angle. Accordingly, flexible microwaveantennas are suitable for use in such oils. Accordingly, the processincludes uncapping a capped oil well. This can be accomplished bydrilling out a concrete plug used to cap the well, if present.

The system can include a number of auxiliary equipment located on thesurface of the ground. Such equipment includes, for example, welldrilling equipment, vacuum pump vehicle, fuel tank vehicles, a generatorvehicle, and microwave control vehicle that includes microwavegenerators, microwave waveguides, and associated equipment. The vacuumpump vehicle can contain a vacuum pump that is capable of applyingintermittent vacuum pulse technology to raise hydrocarbon gases to thesurface. The hydrocarbon gases are recovered and collected in a suitabledistillation tower or fractionation tower that is fitted with heatexchanger and condensing unit. Suitable oil wells and other hydrocarbongeological deposits residing in the ground are accessed via a tube toprovide a sealed system with the vacuum pump vehicle for producing thevacuum environment needed for recovering a hydrocarbon vapors. Suitablevacuums include absolute pressures of less than about 20 mm of mercury,or even less than about 40 mm of mercury, or even less than about 100 mmof mercury. The microwave control vehicle contains suitable flexiblemicrowave waveguides and generators. Typically the end of the microwavewaveguides (e.g., antennas) are fitted with a suitable microwave coneemitter (e.g., nozzle). The antennas are placed into the mahogany zonein Earth in situ and microwaves are used to radiate tar sands, or oilshale, or other hydrocarbon deposits. The microwaves cause vaporizationand gasification of the otherwise viscous and solid-like hydrocarbon andcarbon geological sources within the ground. One or more antenna fittedwith one or more cone emitter devices can be used.

Generated hydrocarbon gases (e.g., take off gases) are transported to asuitable fractionation tower capable of separating the gas, asillustrated in FIG. 5C. Geological material such as sand and rock fromwhich hydrocarbons have been removed remain within the geologicalformation. In some embodiments, an in situ microwave process isprovided. Other embodiments do not require in situ microwave irradiationof the geological formation, e.g., geological material containinghydrocarbons that are mined and provided via separate feed mechanisminto a suitable microwave reactor. Geological material such as sand androck can be substantially totally gasified (i.e., depleted ofhydrocarbons and carbons) according to the processes of the presentinvention, which geological material is then returned to the environmentsubstantially free of hydrocarbons. Finally, fuel and other hydrocarbonsrecovered form the geological source can be stored in a suitable tankervehicle and shipped for delivery, further processing, and so on. Therecovered hydrocarbons may also be transported by pipeline, rail car,and the like. Optionally, the hydrocarbon vapor recovered fromgeological sources may be fractionalized on-site using a suitabledistillation tower, as illustrated in FIG. 5A. The process of operatinga distillation tower is suitably described in FIG. 5C, whichillustration shows the separation of crude oil using a fractionatingtower into its component products.

FIG. 6 depicts one embodiment for extracting petroleum-based materialsfrom shale and tar sands and oil sands. The tar sands can be loaded intothe top of the apparatus, which can be under reduced pressure. Usinggravity and shaking, the tar sands move through the apparatus whilebeing exposed to microwave radiation as described herein. Vaporizedpetroleum-based materials can be captured and collected in separatevessels and refined using methods known in the art. After the materialhas passed through the apparatus, it will be essentially free ofpetroleum-based materials. FIG. 6 provides an elevation view of amultiple microwave reactor system suitable for high volume recovery ofpetroleum, carbon and hydrocarbons (e.g. diesel oil) from minedmaterial, e.g., oil shale, oil sands, coal slag, and tar sands. Thissystem is illustrated having the following equipment: microwavewaveguide 602; microwave antennas 620; vacuum gas line 604; microwavereactors 606—a total of five connected in series; connecting pipe 608between microwave reactors 606; top airlock 610 adjacent to in-feed ofsurface shale and tar sand material; airlock 612 adjacent to dischargeof depleted material; baffles 614 within vertically oriented microwavereactors 606; support structure 630 to support multiple microwavereactors connected in series and adjacent to source of surface shaleand/or tar sands. Mined material enters the system at airlock in-feed610, which minimizes the amount of air entering the system. The systemis also fitted with a suitable vacuum gas line 604 to maintain a vacuumenvironment (vacuum pumping equipment not shown) of up to about 20 mm ofmercury, or even up to about 40 mm of mercury, or even up to about 100mm of mercury. Material enters the first microwave reactors 606 adjacentto the airlock, which material is transported along baffles 614 whilebeing irradiated with microwave radiation through microwave antennas 620(as illustrated in the second through fourth microwave reactors 606).Microwaves irradiate, heat, and crack the hydrocarbons, whichhydrocarbons exit the system via a vacuum gas line 604 (connectionsbetween the microwave reactors 606 in the vacuum gas line 604 notshown). Geological material leaves the topmost microwave reactor 606 andenters a first connecting pipe 608, which partially reacted material istransported to a second microwave reactor 606. The process is repeatedand the material is subsequently transported and irradiated withmicrowaves as it progresses along the series of microwave reactors andconnecting tubes. The processed material eventually arrives at thebottom discharge, where it exits the system through an airlock 612.

Another embodiment of an apparatus of the present invention is depictedin FIG. 7. FIG. 7 is a schematic view of a microwave reactor chamber andsystem for recovering fuel oil from a hydrocarbon-containing source,such as used tires. The system includes the following equipment andfeatures: nitrogen supply 702; nitrogen regulator 704; nitrogen flowvalve 706; nitrogen inlet 708 to microwave reactor chamber 710;microwave reactor chamber 710; infrared thermocouple 712 to measureaverage temperature over irradiated area; nitrogen flow meter 714 forinfrared thermocouple purge (low flow); microwave scattering reflector716; motor 718 for microwave scattering reflector 716; platform 720 forholding hydrocarbon containing materials; irradiation area 722; vacuumoutlet 724; vacuum gauge 726; opening 728 to microwave antennae;microwave source 730 (TVT or magnetron); temperature gauge 732; vaportransfer tube 734; condenser tube 736; cooling coil 740; oil collector742; valve drain 744; vacuum bypass valve 746; vacuum pump 748; flowmeter 750 for TWT nitrogen purge (flow); nitrogen supply lines 752;exhaust 754; exhaust gas flow meter 756; reactor chamber door 760.

FIGS. 8A, 8B and 8C illustrate an embodiment of the present inventionfor incorporating a microwave processing system to process drillingcuttings on an oil drilling platform. FIG. 8A is a plan view of anexemplary oil platform incorporating a drill cuttings microwaveprocessing unit. A suitable placement of a microwave processing unit(further illustrated in FIG. 8C) is provided. FIG. 8B illustrates anelevation view of the oil platform in FIG. 8A. FIG. 8C illustrates avertical and horizontal configurations of the drill cuttings microwaveprocessing unit suitable for use in the oil platform illustrated in FIG.8A.

FIGS. 9A-9C are electron microscope photographs at 60,000 timesmagnification of pyrolytic carbon black material obtained according toExample 3 and using the system illustrated in FIG. 7. The production ofthis material is further described in Example 3, below.

FIGS. 10A-10E illustrate an additional embodiment of a system forprocessing materials containing hydrocarbons. Suitable materials includeshale rock, drilling cuttings, tar sands, plastics, polymeric materials,recycled hydrocarbon-containing materials, refuse, residual oil, slurryoil, hydrocarbon distillation bottoms, and the like. These figuresillustrate the following equipment and features: 1001 microwave tubes,amplifier and waveguides; reactor drum 1004; sealed material in-feed1002 through reactor drum 1004; in-feed screw 1003; rotating dischargescrew 1005; control panel 1006; vacuum pumps 1007; hydraulic drivetransmission system 1008 for rotating reactor drum 1004; shippingcontainer 1009; vacuum release support 1010; drum bearing seal 1012;roller bearings 1014; vacuum port 1016; microwave waveguides 1018entering rotating reactor drum 1004; mixing flight bars 1020 for mixingmaterials within the rotating reactor drum 1004; bearings 1022 by whichmechanism the drum slidably rotates; rotating reactor drum axel 1024 bywhich mechanism the reactor drum rotates through actuation with thehydraulic drive transmission center 1008.

FIG. 10A is an elevation view of a rotating drum reactor system.Material enters the in-feed 1002 via a suitable source, for example ahopper for receiving chips or chunks of material. The material thenenters into the in-feed screw 1003, which meters the material intoreactor drum 1004. The material is stirred and mixed using mixing flightbars 1020. The drum is rotated using the hydraulic drive system 1008.The drum reactor is maintained under vacuum by means of vacuum pumps1007 and vacuum gas line. The reactor drum is vacuum sealed by means ofa drum bearing seal 1012 as shown in the inset of FIG. 10D. Microwavesare generated at 1001 and transmitted by a waveguides 1018 into the drumreactor 1004. Hydrocarbon vapors are removed through the vacuum gas lineand collected for further processing as described herein above.

FIG. 10B is a plan view of the rotating drum reactor portion depicted inFIG. 10A. The rotating drum 1004 is shown comprising a drum bearing seal1012, which drum slidably rotates against end caps comprising ports formicrowave antenna and vacuum connections. The reactor drum slides viaroller bearings 1014 in the top and bottom end caps. The drum reactor1004 resides within shipping container 1009. Screw conveyor 1003 conveysmaterial into the drum reactor 1004. FIG. 10C is a plan view of analternative embodiment of a rotating drum reactor system. FIG. 10D is across-sectional view of a drum bearing seal used in the rotating drumreactor system.

FIG. 10E is an elevation view of the rotating drum reactor portiondepicted in FIG. 10A. FIG. 10E further illustrates the in-feed screw1003 for metering the material into reactor drum 1004, which material isstirred and mixed using mixing flight bars 1020 as the drum is rotatedusing the hydraulic drive system 1008. The drum reactor is maintainedunder vacuum by means of vacuum pumps 1007 and vacuum gas line. Thereactor drum is vacuum sealed by means of a drum bearing seal 1012 asshown in the inset of FIG. 10D. Microwaves are generated at 1001 andtransmitted by waveguides 1018 into the drum reactor 1004. Mixing flightbars 1020 are used for mixing materials within the rotating reactor drum1004. Bearings 1022 are used for slidably rotating the drum whilemaintaining the vacuum and microwave antenna connections. The reactordrum rotates by means of axel 1024 through actuation with the hydraulicdrive transmission center 1008. Hydrocarbon vapors are removed throughthe vacuum gas line 1016 and collected for further processing asdescribed herein above. Spent materials substantially depleted ofhydrocarbons exit to discharge screw 1005.

As an example, a suitable microwave rotating reactor drum system forextracting hydrocarbons from materials such as drill cuttings and fluidscan comprise the following equipment:

A suitable microwave control center includes a number of hydrocarbonspecific modular microwave generators, high power amplifiers, mastercontroller module, slave driven power modules, thermal sensors, safetyI/O devices for vacuum, interlocks, and emergency shut down, manifoldbanked configuration of flexible waveguides/windows/adapter plates,thermal metrology gear microwave power measurement instruments andcomputer control station as per schedule.

A suitable 4′-0″ diameter rotating in-feed channel drum unit with vacuumseal provisions comprises ⅜″ stainless steel welded frame constructionand bolt on stainless steel (replaceable) hardened steel troughs drivenby a direct coupled, 5-hp NEMA-4 variable speed (VFD driven) indexingservo-motor to transfer metered product into the feed screw.

A suitable 2′-6″ diameter×12′-6″ long in-feed screw assembly comprisesheavy-duty stainless steel 2″ square tubing frame supporting ⅜″stainless steel skins with hardened helical screw driven by a directcoupled, 2-hp NEMA-4 variable speed (VFD) servo-motor to transfermetered product into the reactor vessel.

A suitable 5′-0″ diameter×⅜″ horizontal seamlessly welded stainlesssteel and jacketed sub-baric vessel is constructed with internal angularflight bars, (length varies depending on composition of the intendedprocess to) with two-24″ long×⅜″ stainless steel end cap sections,hardened steel circum-centerline rack & pinion hydraulic transmissiondriven by a variable speed gear-head motor. Includes a maintenanceaccess door, piping as required to heat vessel jacket, microwave antennamountings, vacuum port, pressure/flow meters and gauges as required,power transmission is stainless steel guarded. Reactor tank andperipheral equipment is supported by heavy duty stainless steel formedstructural channels and heavy duty external bearing wheels.

A suitable 2′-6″ diameter×12′-6″ long discharge screw assembly comprisesheavy-duty stainless steel 2″ square tubing frame supporting ⅜″stainless steel skins with hardened helical screw driven by a directcoupled, 2-hp NEMA-4 variable speed (VFD) servo-motor to transfermetered product into the reactor vessel.

A suitable NEMA 4 electrical motor control panel, 480 v/3 ph/60 Hz-24volt control circuits controls all motors and devices, directly mountedto shipping container wall, includes Allen-Bradley PLC, touch screendiagnostics, VFD drive components, I/O racks, rigid conduit with allmarine wire specs, color coded, tagged and match-marked for easyidentification.

A suitable vacuum system comprises Dual to Quad (which varies accordingto throughput) 1.5-hp oil-lubricated, rotary vane vacuum pumps systemfor-20 in.Hg. continuous duty operation. A vacuum release port system ismounted on the discharge screw section.

Electron activator. It has been discovered that microwave radiation inthe frequency range of from about 4 GHz to about 12 GHz is useful forselectively recovering hydrocarbon materials from geological petroleumand mineral sources, as well as manufactured materials such asautomobile and truck tires. It has further been found that suchmaterials can comprise carbon particles that absorb energy whenirradiated with microwave radiation. The heat from the energized carbonparticles is released to the adjacent hydrocarbon materials, and whensufficient heat is released, the hydrocarbons are reduced in molecularweight, i.e., “cracked”, and vaporized. Unlike the prior art, thepresent discovery discloses a particular range of frequencies that isefficacious for the electromagnetic stimulation and heating of carbonparticles for recovering hydrocarbons, such as diesel fuel, fromdifficult to recover hydrocarbon sources.

Disclosed are methods for microwave treatment of difficult-to-recoverhydrocarbon source materials comprising contacting the hydrocarbonsource material with particles comprising carbon, and subjecting thehydrocarbon source material to microwave radiation. Also disclosed aremethods for microwave treatment of hydrocarbon source materialcomprising contacting the hydrocarbon source material with materialhaving a resonating frequency in the range of from about 4 GHz to about12 GHz, and subjecting the hydrocarbon source material to microwaveradiation characterized as having at least one frequency component thatcorresponds to the resonating frequency of the material. As used herein,carbon particles or material having a resonating frequency correspondingto the applied microwave radiation frequency are collectively referredto as “electron activator”.

In preferred embodiments of the disclosed methods, the microwaveradiation is one or more pre-selected microwave radiation frequencies.Preferably, the pre-selected microwave radiation frequency will be theresonating microwave frequency, i.e., the microwave radiation frequencyat which the particles comprising carbon absorb a maximum amount ofmicrowave radiation. It has been determined that different compositionsof the present invention will absorb more or less microwave radiation,depending on the frequency of the microwave radiation applied. It hasalso been determined that the frequency at which maximum microwaveradiation is absorbed differs by composition. By using methods known inthe art, a composition of the present invention can be subjected todifferent frequencies of microwave radiation and the relative amounts ofmicrowave radiation absorbed can be determined. Preferably, themicrowave radiation selected is the frequency that comparatively resultsin the greatest amount of microwave radiation absorption. In oneembodiment, the pre-selected microwave radiation frequency ischaracterized as having at least one frequency component in the range offrom about 4 GHz to about 12 GHz. In other embodiments, the pre-selectedmicrowave radiation frequency is characterized as having at least onefrequency component in the range of from about 5 GHz to about 9 GHz,from about 6 GHz to about 8 GHz, or from about 6.5 GHz to about 7.5 GHz.

The particles comprising carbon are preferably carbon substances thathave a resonating microwave frequency of from about 4 GHz to about 12GHz. Many forms of carbon are known by those skilled in the art, and,while not intending to exclude other carbon types, it is contemplatedthat any form of carbon having a resonating microwave frequency of fromabout 4 GHz to about 12 GHz will be within the scope of the presentinvention. For example, the particles comprising carbon can comprisecarbon black. Carbon black may be described as a mixture ofincompletely-burned hydrocarbons, produced by the partial combustion ofnatural gas or fossil fuels.

Carbon blacks have chemisorbed oxygen complexes (e.g., carboxylic,quinonic, lactonic, phenolic groups and others) on their surfaces tovarying degrees depending on the conditions of manufacture. Thesesurface oxygen groups are collectively referred to as the volatilecontent. In preferred embodiments, the present invention uses carbonblack having a moderate volatile content. The volatile content of thepreferred carbon black can be composed of hydrocarbons having up toabout 20 carbon atoms, or even up to about 30 carbon atoms.

The constituent parts of the electron activator preferably havecharacteristic dimensions in the micrometer range, although otherparticle or fragment sizes may also be used. Because carbon particles orparticles comprising another electron activator for use in the presentinvention can be present in numerous configurations, and can beirregular in shape, the term “characteristic dimensions” is used hereinto describe the long axis in the case of substantially cylindrical orotherwise oblong particles, and to describe diameter in the case ofsubstantially spherical particles, etc. In some embodiments wherein thecarbon particles comprise carbon black, the particles can havecharacteristic dimensions of about 10 nm to about 250 μm. In otherembodiments, the particles can have characteristic dimensions of about100 nm to about 100 μm, or of about 200 nm to about 10 μm.

Preferred are electron activators having characteristic dimensions thatare conducive to ready dispersion within hydrocarbon materials that aretargeted for vaporization. The electron activators can be contacted withthe hydrocarbon materials by directly introducing the electronactivators into the hydrocarbon materials environment.

In the present systems, the electron activator particles can compriseany material that is capable of absorbing at least a portion of thetransmitted microwave radiation generated by the microwave generator. Inpreferred embodiments the material comprises carbon. The particlescomprising carbon are preferably carbon substances that have aresonating microwave frequency of from about 4 GHz to about 12 GHz. Manyforms of carbon are known by those skilled in the art, and, while notintending to exclude other carbon types, it is contemplated that anyform of carbon having a resonating microwave frequency of from about 4GHz to about 12 GHz will be within the scope of the present invention.For example, the particles comprising carbon can comprise carbon black.Carbon blacks have chemisorbed oxygen complexes (e.g., carboxylic,quinonic, lactonic, phenolic groups and others) on their surfaces tovarying degrees depending on the conditions of manufacture. Thesesurface oxygen groups are collectively referred to as the volatilecontent. In preferred embodiments, the present invention uses carbonblack having a moderate volatile content prepared by processing tirechips using microwave radiation as described herein above.

The constituent parts of the particles preferably have characteristicdimensions in the micrometer range, although other particle or fragmentsizes may also be used. Because carbon particles or particles comprisinganother electron activator for use in the present invention can bepresent in numerous configurations, and can be irregular in shape, theterm “characteristic dimensions” is used herein to describe the longaxis in the case of substantially cylindrical or otherwise oblongparticles, and to describe diameter in the case of substantiallyspherical particles, etc. In some embodiments wherein the carbonparticles comprise carbon black, the particles can have characteristicdimensions of about 100 μm.

EXAMPLES

The following examples are provided to further describe the presentinvention. They are not to be construed to limit the scope of theinvention described in the claims. Many of the examples make use of theapparatus substantially illustrated and described in FIG. 7.

Example 1

A chamber capable of being subjected to between 4.0 to 12.0 GHz ofmicrowave radiation frequencies and rated to withstand reducedatmospheric pressure, was equipped with a 700 W, 5.8 to 7.0 GHz VFMmicrowave tube (Lambda Technologies, Morrisville, N.C.). The chamber wasoutfitted with a nitrogen gas inlet tube, a vacuum inlet tube, and anoutlet tube connected to a heat exchanger and collection vessel. Thechamber was also equipped with an infrared thermocouple temperatureprobe.

Example 2

A chamber capable of being subjected to between 4.0 to 12.0 GHz ofmicrowave radiation frequencies and rated to withstand reducedatmospheric pressure, was equipped with a 1800 W, 7.3 to 8.7 GHz VFMmicrowave tube (Lambda Technologies, Morrisville, N.C.). The chamber wasoutfitted with an nitrogen gas inlet tube, a vacuum inlet tube, and anoutlet tube connected to a heat exchanger and collection vessel. Thechamber was also equipped with an infrared thermocouple temperatureprobe.

Example 3

A 20 lb automobile tire was cut into approximately 4″×4″ pieces. Thesepieces were washed and dried. The pieces were placed on a tray andloaded into the chamber of Example 1. Twenty psi of N₂ was introducedinto the chamber. The VFM microwave radiation was initiated (700 W,5.8-7.0 GHz). When the temperature of the tire pieces reached 465° F.,the microwave radiation was halted and the tire pieces allowed to coolabout 5-25° F. Microwave radiation was resumed. This process wasrepeated an additional three times. Total experiment run time wasapproximately twelve minutes. The decomposition products were thenanalyzed.

This experiment produced 1.2 gallons of #4 oil (see Tables 1 and 2), 7.5lbs of carbon black, 50 cu. ft. of combustible gases (including methane,ethane, propane, butane, and isobutene), and 2 lbs of steel. FIGS. 9A-9Cdepict electron microscope photographs of samples of carbon blackproduced using this method. FIG. 9C demonstrates that the carbon blackproduced by this method is comparable to commercial-grade rubber black.

TABLE 1 Analysis of Oil Produced by Example 3. TEST RESULT Gross Heat ofCombustion 18308 BTU/lb Gross Heat of Combustion 144688 BTU/gal Sulfur0.931 wt. % Kinematic Viscosity @ 122° F. 9.773 cSt Saybolt FurolViscosity @ 122° F. 78.9 sus Sediment by Extraction 0.02 wt. % Ash @775° C. 0.024 wt. % Nitrogen 0.43 wt. % Samples were tested by ITS CalebBrett, Deer Park, TX. Samples were filtered through a 100 mesh filterprior to testing.

TABLE 2 Analysis of Oil Produced by Example 3 TEST RESULT CorrectedFlash Point 92° C. Corrected Flash Point 198° F. API Gravity 15.56° C.,60° F. 13.7° API Samples were tested by ITS Caleb Brett, Deer Park, TX.

Example 4

A sample of oil cuttings, oil shale, tar sands, oil sands, slurry oil,and/or a material contaminated with petroleum-based materials, is placedin the apparatus of Example 2. The pressure is reduced to 20 Torr.Microwave radiation is applied to the sample for a time sufficient tovaporize all the petroleum-based material in the sample. At 20 Torr, thepetroleum-based materials vaporize between about 400 and 520° F. Thevaporized petroleum-based materials are cooled and collected in acollection vessel. The material remaining in the chamber issubstantially free of petroleum-based material.

Example 5

A plastic bottle was placed in the apparatus of Example 1 and exposed tomicrowave radiation. The exposure to microwave radiation resulted incomplete vaporization of the bottle and recovery of petroleum-basedmaterials.

When ranges are used herein for physical properties, such as molecularweight, or chemical properties, such as chemical formulae, allcombinations, and subcombinations of ranges for specific embodimentstherein are intended to be included.

The disclosures of each patent, patent application, and publicationcited or described in this document are hereby incorporated herein byreference, in its entirety.

Those skilled in the art will appreciate that numerous changes andmodifications can be made to the preferred embodiments of the inventionand that such changes and modifications can be made without departingfrom the spirit of the invention. It is, therefore, intended that theappended claims cover all such equivalent variations as fall within thetrue spirit and scope of the invention.

1. An apparatus for extracting a petroleum-based material from a composite comprising petroleum-based material, comprising: a microwave radiation generator, wherein said generator is capable of applying microwave radiation characterized as having at least one frequency component in the range of from about 4 GHz to about 18 GHz; and at least one container to collect said extracted petroleum-based material.
 2. The apparatus of claim 1, wherein the microwave radiation generator is capable of applying a microwave radiation frequency of between about 4.0 and about 12.0 GHz.
 3. The apparatus of claim 2, wherein the microwave radiation generator is capable of applying a microwave radiation frequency of between about 7.9 and about 8.7 GHz.
 4. The apparatus of claim 1, wherein the microwave radiation generator is capable of applying a sweeping range of microwave radiation frequencies of between about 4.0 and about 12.0 GHz.
 5. The apparatus of claim 4, wherein the range of frequencies of said radiation is in the C-Band frequency range.
 6. The apparatus of claim 4, wherein the range of frequencies of said radiation is in the X-Band frequency range.
 7. The apparatus of claim 4, wherein the range of frequencies of said radiation is in the range of from about 5.8 GHz to about 7.0 GHz.
 8. The apparatus of claim 4, wherein the frequency of said radiation is in the range of from about 7.9 GHz to about 8.7 GHz.
 9. The apparatus of claim 1, further comprising at least one chamber for holding said composition.
 10. The apparatus of claim 1, wherein said chamber is closed to the outside atmosphere.
 11. The apparatus of claim 1, wherein said chamber is capable of operating at an internal pressure of less than about 40 Torr.
 12. The apparatus of claim 1, wherein said chamber is capable of operating at an internal pressure of less than about 20 Torr.
 13. The apparatus of claim 1, wherein said chamber is capable of operating at an internal pressure of less than about 5 Torr.
 14. The apparatus of claim 1, further comprising a temperature detector for said composite. 